JP3020985B2 - Exterior parts having a gold layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention can be used for a gold exterior article, for example, a watch, a band or a jewelry such as a ring, a necklace, glasses, or the like.

[Prior Art] Watches, bands or rings, necklaces, eyeglasses, and other accessories are conventionally made of gold or plated with gold because of its excellent color tone and corrosion resistance. . However, since gold is an expensive metal, forming a thick coating layer having sufficient corrosion resistance and abrasion resistance puts a large economic burden.

In order to reduce this burden, various gold-colored alloys have been conventionally proposed and widely used, but they have not been satisfactory.

At this time, a base layer made of a metal nitride exhibiting a golden color, for example, titanium nitride (hereinafter referred to as TiN) was provided by a method such as ion plating or sputtering, and a finishing layer made of gold or a gold alloy was provided thereon. An exterior component having a gold coating layer has been proposed.

However, the color tone of TiN is monotonous due to its simple composition, and the color tone is greenish-yellow compared to the noble metal gold or gold alloy, so the thickness of the gold coating layer provided on the finishing layer is 0.3 μm.
Otherwise, it may be affected by the color tone of the base layer and may be unsuitable as an exterior product. In addition, when the gold coating layer of the finishing layer is worn out by carrying for a long time and the TiN layer of the base layer is exposed,
In some cases, the golden color of the finish layer may be uncomfortable with the user, which may lead to a complaint from the user.

[Problem to be Solved by the Invention] This invention solves the above-mentioned problems of the prior art, and
It is an object of the present invention to provide an exterior component having a coating layer which can obtain a gold color tone close to that of gold or a gold alloy, has excellent color tone stability, and has high abrasion resistance.

[Means for Solving the Problems] According to the structure of the invention for solving the above problems, the molar ratio between titanium (Ti) and aluminum (Al) is 90:10 to 99:
This is an exterior component having a base layer made of a composite nitride of titanium and aluminum [(Ti-Al) N] and a finishing layer made of gold or a gold alloy provided thereon.

The thickness of the base layer is suitably 0.5 μm, and if it is less than 0.1 μm, color stability cannot be obtained, and there is a problem in corrosion resistance.
If it exceeds μm, there is a risk of generation of microcracks.
A range of approximately 0.1-5.0 μm is suitable.

As a means for forming the base layer, sputtering is suitable, but it can also be formed by ion plating.

This base layer is harder than the conventional TiN layer (Vickers hardness about 1000 HV), and the Vickers hardness is about 2000 HV.
That is all. The data of the TiN layer in the color tone is L ^* 62.8, A ^* 7.0, B ^* 23.5, as indicated by data from a color difference meter. If the color difference meter data of 1N-14 (international standard) of the finishing layer is compared with the numerical values of L ^* 68.5, A ^* 8.0 and B ^* 19.8, the numerical value of TiN gold color tone is small in L ^* , which means that This means that the surface glossiness is reduced and the color tone looks dark.

In A ^* , the value is an approximate value, but the value is slightly smaller, and thus tends to be greenish-yellow. The interaction with L ^* further increases the tendency.

Conversely, B ^* has a large value and a strong yellow tendency. The color tone is black in comparison with 1N-14, which is required for the color appearance, and the color tone is uncomfortable in the visual appearance inspection by 1N-14. For this reason, it is difficult to apply the base layer single layer to the exterior product, and it is essential to apply gold or a gold alloy for the finishing layer.

However, in this case, the finished layer has a thickness of 0 in consideration of economy.
Processing is performed in the range of 1 to 0.3 μm, but the finishing layer is affected by the base layer because it is a thin film, and the color tone differs from the original finishing layer gold or gold alloy color tone, and the color tone varies compared to 1N-14. occured.

In addition, when the mobile phone is carried for a long time, the base layer is exposed due to abrasion of the finishing layer, and the user feels uncomfortable with the color tone of the base layer and the finishing layer. Both of these problems caused the finished layer to be 0.3μ
The solution can be solved by applying m or more, but the economy becomes a problem.

On the other hand, the data obtained by the (Ti-Al) N color difference meter is a typical example, and when the molar ratio of titanium to aluminum is 95: 5, the values are L ^* 70.66, A ^* 1.46, B ^* 28.43. .

If comparing with the numerical value of the 1N-14 color difference meter data, the (Ti-Al) N color tone is small in L ^* ,
This increases the surface glossiness, makes the color sense vivid, and the color tone tends to be pale and white.

In the case of A ^* , the numerical value is small, which means that the green tendency is increased. In B ^* , the value is large and the yellow tendency is strong. However, both A ^* B ^{* and} L ^* are less noticeable due to the interaction with L ^*, and the required 1N
Compared to -14, the visual appearance inspection showed little discomfort. Therefore, gold or a gold alloy applied for the purpose of color adjustment is hardly affected by the base layer, so that the thickness of the finishing layer is extremely thin, for example, even if it is in the range of 0.01 to 0.1 μm, the effect is sufficient, and it is very economical. It is a target.

Also, the base layer is easily exposed due to abrasion of the finishing layer when the device is carried for a long time, but the difference in the color tone is hard to be recognized, and the life of the exterior product is long.

[Examples] Hereinafter, the present invention will be specifically described with reference to examples.

In Examples 1 to 3 below, a composite nitride of Ti and Al was formed by the above method and apparatus by changing the flow rate of N ₂ using a target in which the molar ratio of Ti and Al was kept constant for each example, and the color tone thereof Was measured.

Example 1 As a procedure for producing a (Ti-Al) N thin film, the chamber is evacuated to 5.0 × 10 ⁻⁵ mbar. 8.0 × 10 ^-3 mba of inert gas argon was introduced into the chamber to remove impurities deposited on the target surface by opening to the atmosphere.
Then, pre-sputtering is performed for 1 minute by applying a 417 V DC voltage to the target. Thereafter, the inside of the chamber is evacuated again, and after confirming the degree of vacuum with a vacuum pressure gauge, an inert gas of argon is introduced into the chamber at 1.2 × 10 ⁻² mbar to perform ion bombardment for the purpose of removing impurities deposited on the substrate. A DC voltage of 700 V is applied to the substrate to cause glow discharge, and ion bombardment is performed for 2 minutes. Thereafter, the inside of the chamber is evacuated again.

For a Ti-Al target with a molar ratio of 90:10 [at%], first introduce 3.0 × 10 ⁻³ mbar of argon gas, and then introduce nitrogen gas.
It was introduced up to 3.2 × 10 ⁻³ mbar. Next, a DC voltage of 160 V was applied to the substrate, and subsequently a DC voltage of 415 V was applied to the target to form plasma, and a (Ti-Al) N thin film was formed on the substrate for 5 minutes. (Ti-Al) N produced in this way
The color tone of the thin film was measured using a color difference meter. The results are shown in Table 1 below.

When a value close to the numerical value of the 1N-14 color difference meter of the international standard was selected from the following results, the numerical values L ^* 72.26, A ^* 1.21, and B ^* 25.74 were shown. This value is converted to the value L ^* 87.69 of 1N-14,
Compared with A ^* 1.68 and B ^* 27.36, L ^*, that is, the brightness is lower than 1N-14, that is, the (Ti-Al) N thin film is darker. However, A ^* is almost the same numerical value. B ^* also shows a slightly lower value for the (Ti-Al) N thin film, but the difference from the value of 1N-14 is not large.

When comparing this value with the value of a conventional typical color difference meter of the color tone of TiN, the value of the conventional color difference meter of TiN is L ^* 62.8,
A ^* 7.0 and B ^* 23.5, and both L ^* and B ^* are closer to 1N-14 than TiN. A * is decreasing, indicating that it is less reddish than that of TiN. In other words, the color tone at this time has a color tone that is brighter and less reddish than the gold color of TiN. When the nitrogen gas is changed to a certain flow rate by the above method, the color tones are L ^* 67.95, A ^* 4.59, B ^* 27.28, which are also compared with the values of the conventional TiN. Both L ^* and B ^* show high numerical values. A ^* also shows a lower value than TiN. This is also brighter than the gold color of TiN, and also indicates that redness has been removed. With a Ti—Al target having a molar ratio of 90:10, a golden thin film can be obtained between the above gas flow rates. Although there is a slight difference in the numerical values of the color difference meter, a value closer to 1N-14 than the gold color of TiN can be obtained in this range.

Example 2 A test was performed in which the molar ratio of the Ti—Al target was 95: 5. A new substrate was set in the order described above, pre-sputtered, bombarded, then evacuated again, and argon gas was introduced up to 3.0 × 10 ⁻³ mbar, followed by nitrogen gas introduced up to 3.3 × 10 ⁻³ mbar. did. Thereafter, a DC voltage of 160 V was applied to the substrate, and subsequently a DC voltage of 418 V was applied to the target to produce plasma, and (Ti-Al) N was produced for 5 minutes. The thus obtained (Ti-Al) N thin film was prepared in Example 1.
When measured with the same color difference meter as in Example 1, the values shown in Table 2 below were shown.

Numerical values of one sample L * 70.66, A * 1.46, B ^* 2
When comparing 8.43 with the color difference meter of 1N-14, L ^* is (Ti-
The numerical value of the Al) N thin film is smaller. This indicates that the (Ti-Al) N thin film has slightly lower brightness. A ^* shows almost the same numerical value as 1N-14. B ^* indicates a value close to the value of 1N-14. Also, when this numerical value is compared with the above-mentioned numerical value of TiN, both L ^* and B ^* show higher values than those of TiN. Conversely, A ^* indicates a low numerical value. This indicates that the TiN is less reddish than the gold. When the flow rate of the nitrogen gas is changed to a certain value, the (Ti-Al) N thin film shows the following numerical values. L
^With a target of ^* 70.66, A ^* 1.46, B ^* 28.43, and Ti: Al = 95: 5, a thin film closer to 1N-14 than the gold color of TiN can be obtained in this range.

Example 3 A test was performed by changing the target to a Ti-Al target having a molar ratio of 99: 1. Pre-sputtering and bombardment were performed under the conditions described above, and then argon gas was introduced to 3.0 × 10 ⁻³ mbar, and subsequently nitrogen gas was introduced to 3.3 × 10 ⁻³ mbar. Then apply a DC voltage of 160V to the substrate, and then apply
A 416 V DC voltage was applied to produce a (Ti-Al) N thin film for 5 minutes. The obtained (Ti-Al) N thin film was measured using the same color difference meter. The results are shown in Table 3 below.

The measured values of one sample are L ^* 75.01, A ^* 2.31, and B * 31.27. When this numerical value is compared with the value of a color difference meter of 1N-14, L * indicates a slightly lower brightness. A ^* indicates a numerical value higher than the value of 1N-14. This indicates that it has more redness than 1N-14. B ^* indicates a higher value than that of 1N-14, which indicates that it has a yellow tint. When these numerical values are compared with the above-mentioned values of the color difference meter for TiN, both L ^* and B ^* show higher numerical values than the value of TiN. This indicates that it is brighter and yellower than TiN. A ^* is considerably lower than the value of TiN, meaning that there is little redness. When the flow rate of the nitrogen gas is changed within a certain range, the (Ti-Al) N thin film shows the following numerical values. L ^* 71.37, A ^* 5.48, B ^* 2
In a Ti-Al target having a molar ratio of 9.86 and a molar ratio of 99: 1, a gold color closer to 1N-14 than a gold color of TiN can be obtained in this range.

[Effect of the Invention] As described above, the exterior product of the present invention has a small variation in the color tone of the product even when the formation conditions of the base layer vary, and
Since the hardness of the base layer is also sufficiently high, it is an exterior product with excellent color tone and long life.

[Brief description of the drawings]

1 to 3 are graphs showing the results of the color tone measurement of the sample of the embodiment of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-153776 (JP, A) JP-A-62-182267 (JP, A) JP-A-58-4116 (JP, A) 36552 (JP, B2) (58) Field surveyed (Int. Cl. ⁷ , DB name) C23C 14/00-14/58 A44C 5/00 B44C 1/14

Claims (1)

(57) [Claims] 1. The method of claim 1, wherein the molar ratio of titanium to aluminum is 90: 1.
A base layer made of a composite nitride of titanium and aluminum in the range of 0 to 99: 1, and a gold layer characterized by having a finishing layer made of gold or a gold alloy for color tone adjustment provided thereon. Exterior parts to have.